US1339947A - Process of making ethyl sulfates - Google Patents
Process of making ethyl sulfates Download PDFInfo
- Publication number
- US1339947A US1339947A US309027A US30902719A US1339947A US 1339947 A US1339947 A US 1339947A US 309027 A US309027 A US 309027A US 30902719 A US30902719 A US 30902719A US 1339947 A US1339947 A US 1339947A
- Authority
- US
- United States
- Prior art keywords
- ethyl
- sulfuric acid
- sulfate
- ethylene
- making
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 16
- 150000005452 ethyl sulfates Chemical class 0.000 title description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 33
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 16
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 16
- 239000005977 Ethylene Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids
Description
UNITED STATES. PATENT OFFICE.
HENRY R. CURME, OF PITTSBURGH, PENNSYLVANIA, ASSIGNOR T UNION CARBIDE COMPANY, OF NEW YORK, N. Y.. A CORPORATION OF VIRGINIA.
PROCESS OF MAKING ETHY L SULFATES.
No Drawing;
1 To all whom it ma concern:
Be it known t at I, HENRY R. CURME,
a citizen of the United States, residing at Pittsburgh, in the countyof Allegheny and State of Pennsylvania, have invented certain new and useful Improvements in Processes of Making Ethyl Sulfates, of which the following is a specification.
It is known that alcohol may be synthesized from ethylene by a process involving the successive steps of absorbing ethylene in concentrated sulfuric acid (98100%) to form ethyl hydrogen sulfate, and then hydroly'zing this ester with formation of alcohol and dilute sulfuric acid. The reactions involved in this known process are usually expressed as follows It is also known that ether may be prepared from the ethyl hydrogen sulfate by reacting thereon with alcohol, according to the reaction absorbed by the'sul u'ric acid in a single passage therethrough, there is produced in addition to ethyl hydrogen sulfate and simultaneously therewith, a certain propor- .tion of di-ethyl sulfate (G H SO This substance is formed before the sulfuric acid has been completely transformed into ethyl hydrogen sulfate, and can be produced in and removed froni the solution while sulfuric acid still remains therein in an uncombined state. Di-ethyl sulfate has a higher vapor tension at .the reacting temperature than either ethyl hydrogen sulfate or sulfuric acid, and by suitable-control of the. temperature and of the volume of Specification of Letters Patent. Patented May 11 1920, Application filed July 7, 1919. Serial No. 309,027.
ter is somewhat weakened, some water is found to be entrained with the'current of ethylene and to collect in the condenser with the di-ethyl ester. Since, however, the latter" is immiscible with water, it is-easily parted and recovered in a state of substantial purity. It follows from the above that the sulfuric acid used undergoes actual concentration in the process and at the reacting temperature, which may be considerably varied but should not exceed 150 C. This permits me to start the operation with relatively dilute sulfuric .acid, as compared with the very high concentrations (98100 H 80 which-have heretofore always been regarded as an essential condition for the ethylene absorption. As will be readily understood this effects a very great economy in the process, since the dilute acid resulting from the subsequent hydrolysis of the ethyl hydrogen sulfate, or of the di-ethyl sulfate,
may be readily and cheaply re-concentrated to about 66 B., and is then suitable for use in continuing or repeating the process. Furthermore, to the extent that di-ethyl sulfate is formed a further economy of sulfuric acid is of course brought about, since the proportion of acid required for the formation of this ester is only one-half of that needed for making ethyl hydrogen sulfate.
While my invention is not limited to the details of procedure below set forth, I now prefer to proceed substantially as follows:
Ethylene in'a state of substantial purity and practically free from diluting gases is injected into and brought into intimate contact with a bath of sulfuric acid having an initial concentration of about 93% H SO The desired intimacy of contact may be brought about by agitation of the bath or by minute subdivision of the gas in any desired manner. The bath is pref,
enel erably maintained at about 100 0., more or. less, and a strong current of ethylene is used, the efiluent gas being passed first to a condenser and then returned through the circulating system to the acid bath, suflicient ethylene being introduced from an outside source to maintain the desired volume of flow. For the best economy in the process the ethylene should be practically free from inert gases, in order that continuous circulation may be maintained without the necessity of discarding any portion of the gas.
The reaction carried out as above is unusually elastic in the sense that any desired proportion of di-ethyl sulfate may be obtained, depending upon-the .duration of treatment of the sulfuric acid with the ethyl- If the ethylene is passed through the acid for a few hours only, say 5 6 hours, a relatively small proportion of the absorbed ethylene usually about 10-15%, will be found to have been transformed into and recovered as di-ethyl sulfate, the principal portion of the absorbed ethylene remaining in the reaction vessel, substantially as ethyl hydrogen sulfate, together with some diethyl sulfate which has not been entrained, and more or less unchanged sulfuric acid. However, as the passage of ethylene is continued, more and more di-ethyl sulfate is formed and carried over to the condense so that eventually practically all of the sulfuric acid may, if desired, be transformed into pure di-ethyl sulfate. In this manner the process may be made to yield almost entirely ethyl hydrogen sulfate, or, almost entirely di-ethyl sulfate, or any desired proportion of these esters.
The di-ethyl sulfate may be utilized directly for the production of alcohol and ether'by hydrolysis, the resulting sulfuric acid being re-concentrated to 66B. and reused in the process. The di-ethyl ester may anddi-ethyl sulfate, entraining di-ethyl sulfate with the excess of ethylene, and separating it therefrom.
3; In a process of making di-ethyl sulfate, the steps comprising passing ethylen'e in excess in contact with sulfuric acid, entraining with the efiluent gas a portion at least of the di-ethyl sulfate resulting from the reaction, and recovering the same.
4:. In a process of making di-ethyl sulfate, the steps comprising passing ethylene in excess in contact with sulfuric acid having an initial concentration approximating 93% H 30 entraining with the effluent gas a portion at least of the di-ethyl sulfate resulting from the reaction and recovering the same.
5. In a cyclical process of making ethyl sulfates or derivatives thereof, the steps comprising passing substantially undilutedv ethylene in excess in contact with sulfuric acid having an initial concentration approximating 93% H S'O ,hydro1yzing the resulting ethyl esters with formation of relatively dilute sulfuric acid, and re-concentrating the sulfuric acid to approximately the said initial concentration for re-use in the process.
In testimony whereof I aflixm si ature.
. HENRY R. ME.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US309027A US1339947A (en) | 1919-07-07 | 1919-07-07 | Process of making ethyl sulfates |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US309027A US1339947A (en) | 1919-07-07 | 1919-07-07 | Process of making ethyl sulfates |
Publications (1)
Publication Number | Publication Date |
---|---|
US1339947A true US1339947A (en) | 1920-05-11 |
Family
ID=23196355
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US309027A Expired - Lifetime US1339947A (en) | 1919-07-07 | 1919-07-07 | Process of making ethyl sulfates |
Country Status (1)
Country | Link |
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US (1) | US1339947A (en) |
-
1919
- 1919-07-07 US US309027A patent/US1339947A/en not_active Expired - Lifetime
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